Ink, ink jet recording method and azo compound

ABSTRACT

An ink containing at least one dye represented by formula (1):  
                 
 
     wherein R 1 , R 2  and R 3  are each independently a hydrogen atom or a monovalent group; Z is a nitrogen atom, or a carbon atom to which a hydrogen atom or a monovalent group is bonded; and at least one of R 1 , R 2 , R 3 , and the monovalent group that Z has is a substituent having a heterocyclic group substituted with an azo group.

FIELD OF THE INVENTION

[0001] The present invention relates to an azo dye, an ink comprisingthe dye which is used for image-forming or the like, an ink jetrecording method, a thermosensitive recording material, a color toner,and a color filter.

BACKGROUND OF THE INVENTION

[0002] In recent years, in particular, materials for forming a colorimage have been mainly used as an image recording material.Specifically, recording materials of ink jet system, recording materialsof heat-sensitive transfer system, recording materials ofelectrophotographic system, silver halide photosensitive materials oftransfer system, printing inks, recording pens, and the like, have beenused extensively. Color filters are used in image pick-up elements, suchas CCD for photographing equipment, and in displays, such as LCD andPDP, to record and reproduce color images.

[0003] In these color image recording materials and color filters, dyes(dyestuffs or pigments) of three primary colors based on a so-calledadditive color mixing method or subtractive color mixing method areused, to display or record full-color images. A dye, which hasabsorption characteristics that enable the acquisition of a preferredcolor reproduction range and has (color)fastness against variousconditions for use and environmental conditions, is not available yet,and improvement is strongly desired.

[0004] Because of inexpensive material costs, capability of high-speedrecording, reduced noise in recording operations, and ease in colorrecording, ink-jet recording has rapidly come into wide use and is beingfurther developed.

[0005] Ink jet recording methods include a continuous method in whichdroplets are supplied continuously and an on-demand method in whichdroplets are supplied in response to an image information signal. Inkdischarge systems include: 1) one in which droplets are discharged byapplying pressure with a piezoelectric element, 2) one in which dropletsare discharged by producing air bubbles in ink with heat, 3) one usingultrasonic waves, and 4) one in which droplets are discharged byelectrostatic suction. Aqueous ink, oil-based ink, and solid (molten)ink are used as ink-jet-recording ink.

[0006] The properties required for a dye that is used in theink-jet-printing ink are: good solubility or dispersibility in asolvent; capability of high-density recording; good hue; fastness tolight, heat, an active gas in environment (e.g. oxidative gases such asozone, NOx, as well as SOx); excellent fastness to water and chemicals;good fixation and little blur on image-receiving materials; excellentstorability as ink; being free from toxicity; high purity; and beingavailable inexpensively. However, it is very difficult to provide a dyethat satisfies these requirements on a high level. Particularly, it isstrongly desired that a dye should have a good yellow hue, and fastnessto light, humidity and heat, and in particular, fastness to an oxidizinggas such as ozone existent in environment when it is printed on animage-receiving material having an ink-receiving layer containing porouswhite inorganic pigment particles.

[0007] Generally, toners containing a colorant dispersed in resinparticles are widely used in color copiers and color laser printers ofelectrophotographic system. The properties required for the color tonersinclude absorption characteristics that enable the acquisition of apreferred color reproduction range, high transmission (transparency)which becomes a problem in particular, when they are used in an overhead projector (hereinafter abbreviated to OHP); and (color)fastnessagainst various factors under environmental conditions when using.Toners containing a pigment as a colorant dispersed in particles aredisclosed in JP-A-62-157051 (“JP-A” means unexamined published Japanesepatent application), JP-A-62-255956 and JP-A-6-118715. Although thesetoners have excellent light resistance, they easily aggregate since theyare insoluble in a solvent, thereby causing problems such as a reductionin transparency and a change in hue of transmitted color. On the otherhand, toners containing a dye as a colorant are disclosed inJP-A-3-276161, JP-A-7-209912 and JP-A-8-123085. These toners have ratherhigh transparency and have no change in hue but have a problem withlight resistance.

[0008] Heat-sensitive transfer recording has advantages, for example,that an apparatus thereof is small in size and can be reduced inproduction cost, that its operation and maintenance are easy, and thatits running cost is low. The properties required for dyes used inthermosensitive transfer recording include absorption characteristicsthat enable the acquisition of a preferred color reproduction range,compatibility between thermal migration and fixability after transfer,thermal stability, and various types of colorfastness of the obtainedimage. Conventionally known dyes satisfy not all of these properties.For example, JP-A-60-2398 proposes a heat-sensitive transfer recordingmaterial and an image-forming method, which chelate-form a thermallydiffusible dye by means of transition metal ions previously added to animage-receiving material, for the purpose of improving fixability andlight resistance. However, the formed chelate dye has absorptioncharacteristics at an unsatisfactory level and involves an environmentalproblem because a transition metal is used.

[0009] Since a color filter needs to have high transparency, a methodcalled a dyeing method, in which the color filter is colored with a dye,has been carried out. For instance, a photoresist which can be dyed issubjected to pattern exposure and development to form a pattern, andthen the resulting pattern is dyed with a dye of filter color.Subsequently, these steps are repeated for all the colors of the filter,to produce a color filter. Besides the above dyeing method, a colorfilter can also be produced by a method using a positive-type resist asdisclosed in U.S. Pat. No. 4,808,501 and JP-A-6-35182. These methodsprovide a color filter which has high transmittance due to use of a dye,thereby being excellent in optical characteristics, but which haslimitation, for example, to light resistance and heat resistance.Therefore, a dye which has excellent resistance to various factors andhigh transparency has been desired. Meanwhile, a method of using anorganic pigment having excellent light resistance and heat resistance inplace of a dye is widely known, but a color filter employing a pigmenthardly gives optical properties equivalent to those when employing adye.

[0010] Dyes for use in the above various applications must have thefollowing properties in common. That is, they must have, for example,absorption characteristics preferred from the viewpoint of colorreproduction, colorfastness under environmental conditions when they areused, such as light resistance, heat resistance, humidity resistance,resistance to an oxidizing gas such as ozone, and satisfactory fastnessagainst chemicals such as a sulfurous acid gas.

[0011] In particular, dyes, which have a good yellow hue andcolorfastness against light, moist heat and active gas contained inenvironment, particularly an oxidizing gas such as ozone, are stronglydesired.

[0012] The typical skeleton of a yellow dye used in ink jet recordinginks is an azo dye skeleton.

[0013] Typical examples of the azo dye include an aminopyrazole azo dyeand a pyrazolone azo chelate dye disclosed in JP-A-57-5770 andJP-A-58-147470, a pyrazolone azo dye disclosed in JP-A-57-642775, apyridone azo dye disclosed in JP-A-6-184481, stilbene azo dyes disclosedin JP-A-5-255625 and JP-A-5-331396, and a bisazo dye disclosed inJP-A-57-65757. JP-A-2-24191 discloses a thiadiazole-azo-pyrazole dye forthermal transfer. Further, in J. Soc. Dyers & Colourists, 102, 176-181(1986), a dye having a triazinyl pyrazole skeleton is described, but itsapplication to ink jet recording inks, heat-sensitive transfer inksheets, color toners, and color filters is not disclosed therein.

[0014] These dyes are discolored or faded by oxidizing gases such asnitrogen oxide gas and ozone, which are often discussed as anenvironmental issue these days, with the result of a reduction inprinting density. There are a large number of dyes that are not alwayssatisfactory in terms of light resistance.

[0015] If the application field of the dyes is expanding and the dyesare widely used in exhibits such as advertisements in the future, itwill be often exposed to light, heat, humidity and an active gascontained in environment. Therefore, a dye, which exhibits an excellenthue, and high fastness to light, moist heat, and an active gas inenvironment (e.g. an oxidizing gas such as NOx and ozone as well as SOx,etc.), and an ink composition of the dye, will be more and more stronglydesired.

[0016] However, it is extremely difficult to find an azo dye and ayellow ink, which satisfy these requirements on a high level.

SUMMARY OF THE INVENTION

[0017] The present invention is an ink, which comprises at least one dyerepresented by formula (1):

[0018] wherein R¹, R² and R³ are each independently a hydrogen atom or amonovalent group; Z is a nitrogen atom, or a carbon atom to which ahydrogen atom or a monovalent group is bonded; and at least one of R¹,R², R³, and the monovalent group that Z has is a substituent having aheterocyclic group substituted with an azo group.

[0019] Further, the present invention is an ink-jet-recording method,which comprises the step of: forming an image with the above-describedink, on an image-receiving material having an ink-receiving layercontaining white inorganic pigment particles on a support.

[0020] Further, the present invention is a compound represented byformula (3):

[0021] wherein R¹⁰ is a hydrogen atom, an alkyl group, a cycloalkylgroup, an aralkyl group, an alkoxy group or an aryl group; R¹¹ is ahydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, anamino group, a sulfo group or a heterocyclic group; Het is an aromaticheterocyclic group; and R¹² is a hydrogen atom, a halogen atom, ahydroxyl group, an alkoxy group, an amino group, a sulfo group, aheterocyclic group, or a group represented by formula (3-1):

[0022] wherein, in formula (3-1), R^(10a) is a hydrogen atom, an alkylgroup, a cycloalkyl group, an aralkyl group, an alkoxy group or an arylgroup; and Het is an aromatic heterocyclic group; and

[0023] in the formula (3), each group on the compound may have asubstituent.

[0024] Other and further features and advantages of the invention willappear more fully from the following description.

DETAILED DESCRIPTION OF THE INVENTION

[0025] According to the present invention, there are provided thefollowing means:

[0026] (1) An ink, comprising at least one dye represented by formula(1):

[0027] wherein R¹, R² and R³ are each independently a hydrogen atom or amonovalent group; Z is a nitrogen atom, or a carbon atom to which ahydrogen atom or a monovalent group is bonded; and at least one of R¹,R², R³, and the monovalent group that Z has is a substituent having aheterocyclic group substituted with an azo group. (Herein, thesubstituent having a heterocyclic group substituted with an azo groupincludes a heterocyclic group itself that is substituted with an azogroup.)

[0028] (2) The ink according to the above item (1), wherein, in formula(1), one of R¹, R² and R³ represents a substituent having a heterocyclicgroup substituted with an azo group.

[0029] (3) The ink according to the above item (1), wherein, in formula(1), at least two of R¹, R² and R³ each represent a substituent having aheterocyclic group substituted with an azo group.

[0030] (4) The ink according to the above item (1), wherein the dyerepresented by formula (1) is a dye represented by formula (2):

[0031] wherein R⁴ is a monovalent group; R⁵ is a group —OR⁸ or a group—NHR⁹; R⁸ and R⁹ are each independently a hydrogen atom or a monovalentgroup; R⁶ is a hydrogen atom or a monovalent group; Ar is an aryl groupor a heterocyclic group; and R⁷ is a hydrogen atom, a monovalent group,or a group represented by formula (2-1):

[0032] wherein, in formula (2-1), R^(4a) is a monovalent group; R^(5a)is a group —OR^(8a) or a group —NHR^(9a); R^(8a) and R^(9a) are eachindependently a hydrogen atom or a monovalent group; and Ar₂ is an arylgroup or a heterocyclic group.

[0033] (5) The ink according to the above item (4), wherein, in formula(2), R⁷ is a hydrogen atom or a monovalent group.

[0034] (6) The ink according to the above item (4), wherein, in formula(2), R⁷ is a group represented by the formula (2-1).

[0035] (7) The ink according to the above item (1), wherein the dyerepresented by formula (1) is a dye represented by formula (3):

[0036] wherein R¹⁰ is a hydrogen atom, an alkyl group, a cycloalkylgroup, an aralkyl group, an alkoxy group or an aryl group; R¹¹ is ahydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, anamino group, a sulfo group or a heterocyclic group; Het is an aromaticheterocyclic group; and R¹² is a hydrogen atom, a halogen atom, ahydroxyl group, an alkoxy group, an amino group, a sulfo group, aheterocyclic group, or a group represented by formula (3-1):

[0037] wherein, in formula (3-1), R^(10a) is a hydrogen atom, an alkylgroup, a cycloalkyl group, an aralkyl group, an alkoxy group or an arylgroup; and Het is an aromatic heterocyclic group;

[0038] in the formula (3), each group on the dye may have a substituent.

[0039] (8) The compound according to the above item (7), wherein, informula (3), R¹² is a hydrogen atom, a halogen atom, a hydroxyl group,an alkoxy group, an amino group, a sulfo group or a heterocyclic group.

[0040] (9) The compound according to the above item (7), wherein, informula (3), R¹² is a group represented by the formula (3-1).

[0041] (10) The ink according to any one of the above items (1) to (9),which is an ink for ink jet.

[0042] (11) An ink-jet-recording method, comprising the step of: formingan image with the ink of any one of the above items (1) to (10), on animage-receiving material having an ink-receiving layer containing whiteinorganic pigment particles on a support (base).

[0043] (12) An ink sheet, comprising at least one dye represented by theformula (1), (2) or (3) according to any one of the above items (1) to(10).

[0044] (13) A color toner, comprising at least one dye represented bythe formula (1), (2) or (3) according to any one of the above items (1)to (10).

[0045] (14) A color filter, comprising at least one dye represented bythe formula (1), (2) or (3) according to any one of the above items (1)to (10).

[0046] (15) A compound represented by the formula (3).

[0047] (16) The compound according to the above item (15), wherein, informula (3), R¹² is a hydrogen atom, a halogen atom, a hydroxyl group,an alkoxy group, an amino group, a sulfo group or a heterocyclic group.

[0048] (17) The compound according to the above item (15), wherein, informula (3), R¹² is a group represented by the formula (3-1).

[0049] (18) A compound represented by formula (4):

[0050] wherein R¹⁰ is a hydrogen atom, an alkyl group, a cycloalkylgroup, an aralkyl group, an alkoxy group or an aryl group; R¹¹ is ahydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, anamino group, a sulfo group or a heterocyclic group; one of X and Y is anitrogen atom and the other is a —C(—R¹³)═ group; R¹³ is a hydrogenatom, a halogen atom, a cyano group, an alkyl group, an alkylthio group,an alkylsulfonyl group, an alkylsulfinyl group, an alkyloxycarbonylgroup, a carbamoyl group, an alkoxy group, an aryl group, an arylthiogroup, an arylsulfonyl group, an arylsulfinyl group, an aryloxy group oran acylamino group; and R¹² is a hydrogen atom, a halogen atom, ahydroxyl group, an alkoxy group, an amino group, a sulfo group, aheterocyclic group, or a group represented by formula (4-1):

[0051] wherein, in formula (4-1), R^(10a) is a hydrogen atom, an alkylgroup, a cycloalkyl group, an aralkyl group, an alkoxy group or an arylgroup; and X and Y have the same meanings as those in formula (4); and

[0052] in the formula (4), each group on the compound may have asubstituent.

[0053] (19) The compound according to the above item (18), wherein, informula (4), R¹² is a hydrogen atom, a halogen atom, a hydroxyl group,an alkoxy group, an amino group, a sulfo group or a heterocyclic group.

[0054] (20) The compound according to the above item (18), wherein, informula (4), R¹² is a group represented by the formula (4-1).

[0055] The present inventors have keenly studied pyrazolyl azo dyederivatives, for seeking a dye having a good hue and high fastness tolight, ozone, and humid and heat. As a result, the inventors have foundthat the above-mentioned problems in the conventional technique can besolved by using a compound represented by the above formula (1) of aspecific dye structure hitherto unknown. Based on this finding, theinventors have completed the present invention.

[0056] The present invention will be described in detail hereinbelow.

[0057] (Azo Dye)

[0058] The azo dye for use in the present invention is represented bythe above formula (1). The formula (1) will be described in detailhereinbelow. The monovalent group in the present invention has the samemeaning as the substituent that an aryl group has, which is describedhereinafter. The heterocyclic group having an azo group has the samemeaning as that represented by Ar in formula (2) or Ar₂ in formula(2-1), and it is preferably a pyrazole ring.

[0059] The azo dye is more preferably an azo dye represented by formula(2). The aryl group represented by Ar or Ar₂ has the same meaning as anaryl group described hereinafter. The heterocyclic group represented byAr or Ar₂ is preferably a 5-membered or 6-membered ring and may becondensed to another ring. The heterocyclic group may be an aromaticheterocyclic or non-aromatic heterocyclic group. Examples of theheterocyclic group include pyridine, pyrazine, pyrimidine, pyridazine,triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine,quinoxaline, pyrrole, indole, furan, benzofuran, thiophene,benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole,benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole,thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine,piperazine, imidazolidine and thiazoline. An aromatic heterocyclic groupis more preferred. Similarly to the above, preferred examples of thearomatic heterocyclic group include pyridine, pyrazine, pyrimidine,pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole,thiazole, benzothiazole, isothiazole, benzisothiazole and thiadiazole.Thiadiazole is the most preferred. Each of these may have a substituent.Examples of the substituent are the same as the substituent on the arylgroup to be described later.

[0060] The azo dye is more preferably a dye represented by the formula(3).

[0061] The formula (3) will be described in detail hereinbelow. Thealkyl group represented by R¹⁰ or R^(10a) includes a substituted orunsubstituted alkyl group. The substituted or unsubstituted alkyl groupis preferably an alkyl group having 1 to 30 carbon atoms. Examples ofthe substituent are the same as the substituent on the aryl group to bedescribed later. Out of these, a hydroxyl group, an alkoxy group, acyano group, a halogen atom, a sulfo group (which may be in the form ofa salt), and a carboxyl group (which may be in the form of a salt) arepreferred. Examples of the alkyl group include a methyl group, an ethylgroup, a butyl group, a t-butyl group, a n-octyl group, an eicosylgroup, a 2-chloroethyl group, a hydroxyethyl group, a cyanoethyl groupand a 4-sulfobutyl group.

[0062] The cycloalkyl group represented by R¹⁰ or R^(10a) in formula (3)includes a substituted or unsubstituted cycloalkyl group. Thesubstituted or unsubstituted cycloalkyl group is preferably a cycloalkylgroup having 5 to 30 carbon atoms. Examples of the substituent are thesame as the substituent of the aryl group to be described later.Examples of the cycloalkyl group include a cyclohexyl group, acyclopentyl group and a 4-n-dodecylcyclohexyl group.

[0063] The aralkyl group represented by R¹⁰ or R^(10a) in formula (3)includes a substituted or unsubstituted aralkyl group. The substitutedor unsubstituted aralkyl group is preferably an aralkyl group having 7to 30 carbon atoms. Examples of the substituent are the same as thesubstituent of the aryl group to be described later. Examples of thearalkyl group include a benzyl group and a 2-phenethyl group.

[0064] The alkoxy group represented by R¹⁰ or R^(10a) in formula (3)includes a substituted or unsubstituted alkoxy group. The substituted orunsubstituted alkoxy group is preferably an alkoxy group having 1 to 30carbon atoms. Examples of the substituent are the same as thesubstituent of the aryl group to be described later. Examples of thealkoxy group include a methoxy group, an ethoxy group, an isopropoxygroup, an n-octyloxy group, a methoxyethoxy group, a hydroxyethoxy groupand a 3-carboxypropoxy group.

[0065] Examples of the aryl group represented by R¹⁰ or R^(10a) informula (3) include a substituted or unsubstituted aryl group. Thesubstituted or unsubstituted aryl group is preferably an aryl grouphaving 6 to 30 carbon atoms. Examples of substituents on the aryl grouprepresented by R¹⁰ or R^(10a) in formula (3) include a halogen atom, analkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, analkynyl group, an aryl group, a heterocyclic group, a cyano group, ahydroxyl group, a nitro group, a carboxyl group, an alkoxy group, anaryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxygroup, a carbamoyloxy group, an alkoxycarbonyloxy group, anaryloxycarbonyloxy group, an amino group (including an anilino group),an acylamino group, an aminocarbonylamino group, an alkoxycarbonylaminogroup, an aryloxycarbonylamino group, a sulfamoyl amino group, an alkyl-or aryl-sulfonylamino group, a mercapto group, an alkylthio group, anarylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfogroup, an alkyl- or aryl-sulfinyl group, an alkyl- or aryl-sulfonylgroup, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group,a carbamoyl group, an imido group, a phosphino group, a phosphinylgroup, a phosphinyloxy group, a phosphinylamino group and a silyl group.

[0066] The aryl group represented by R¹⁰or R^(10a), in particularexamples of a substituent thereon, will be described in detailhereinafter.

[0067] Examples of the halogen atom include a chlorine atom, a bromineatom and an iodine atom, and the alkyl group, alkoxy group, cycloalkylgroup and aralkyl group have the same meanings as defined hereinabove.

[0068] The alkenyl group is a linear, branched or cyclic, substituted orunsubstituted alkenyl group. The alkenyl group is preferably asubstituted or unsubstituted alkenyl group having 2 to 30 carbon atoms.Examples of the alkenyl group include a vinyl group, an allyl group, aprenyl group, a geranyl group, an oleyl group, a 2-cyclopenten-1-ylgroup and a 2-cyclohexen-1-yl group.

[0069] The alkynyl group is preferably a substituted or unsubstitutedalkynyl group having 2 to 30 carbon atoms. Examples of the alkynyl groupinclude an ethynyl group and a propargyl group.

[0070] The aryl group is preferably a substituted or unsubstituted arylgroup having 6 to 30 carbon atoms. Examples of the aryl group include aphenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl groupand an o-hexadecanoylaminophenyl group.

[0071] The heterocyclic group is preferably a 5-membered or 6-membered,substituted or unsubstituted monovalent group obtained by removing onehydrogen atom from an aromatic or non-aromatic heterocyclic compound,more preferably a 5-membered or 6-membered aromatic heterocyclic grouphaving 3 to 30 carbon atoms. Examples of the heterocyclic group includea 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group and a2-benzothiazolyl group.

[0072] The aryloxy group is preferably a substituted or unsubstitutedaryloxy group having 6 to 30 carbon atoms. Examples of the aryloxy groupinclude a phenoxy group, a 2-methylphenoxy group, a 4-t-buthylphenoxygroup, a 3-nitrophenoxy group and a 2-tetradecanoylaminophenoxy group.

[0073] The silyloxy group is preferably a silyloxy group having 3 to 20carbon atoms. Examples of the silyloxy group include a trimethylsilyloxygroup and a t-butyldimethylsilyloxy group.

[0074] The heterocyclic oxy group is preferably a substituted orunsubstituted heterocyclic oxy group having 2 to 30 carbon atoms.Examples of the heterocyclic oxy group include a 1-phenyltetrazole-5-oxygroup and a 2-tetrahydropyranyloxy group.

[0075] The acyloxy group is preferably a formyloxy group, a substitutedor unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, ora substituted or unsubstituted arylcarbonyloxy group having 6 to 30carbon atoms. Examples of the acyloxy group include a formyloxy group,an acetyloxy group, a pivaloyloxy group, a stealoyloxy group, abenzoyloxy group and a p-methoxyphenylcarbonyloxy group.

[0076] The carbamoyloxy group is preferably a substituted orunsubstituted carbamoyloxy group having 1 to 30 carbon atoms. Examplesof the carbamoyloxy group include an N,N-dimethylcarbamoyloxy group, anN,N-diethylcarbamoyloxy group, a morpholinocarbonyloxy group, anN,N-di-n-octylaminocarbonyloxy group and an N-n-octylcarbamoyloxy group.

[0077] The alkoxycarbonyloxy group is preferably a substituted orunsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms.Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxygroup, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group and an-octylcarbonyloxy group.

[0078] The aryloxycarbonyloxy group is preferably a substituted orunsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms.Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxygroup, a p-methoxyphenoxycarbonyloxy group and ap-n-hexadecyloxyphenoxycarbonyloxy group.

[0079] The amino group is preferably a substituted or unsubstitutedalkylamino group having 1 to 30 carbon atoms, or a substituted orunsubstituted anilino group having 6 to 30 carbon atoms. Examples of theamino group include an amino group, a methylamino group, a dimethylaminogroup, an anilino group, an N-methyl-anilino group and a diphenylaminogroup.

[0080] The acylamino group is preferably a formylamino group, asubstituted or unsubstituted alkylcarbonylamino group having 1 to 30carbon atoms, or a substituted or unsubstituted arylcarbonylamino grouphaving 6 to 30 carbon atoms. Examples of the acylamino group include aformylamino group, an acetylamino group, a pivaloylamino group, alauroylamino group, a benzoylamino group and a3,4,5-tri-n-octyloxyphenylcarbonylamino group.

[0081] The aminocarbonylamino group is preferably a substituted orunsubstituted aminocarbonylamino group having 1 to 30 carbon atoms.Examples of the aminocarbonylamino group include a carbamoylamino group,an N,N-dimethylaminocarbonylamino group, anN,N-diethylaminocarbonylamino group and a morpholinocarbonylamino group.

[0082] The alkoxycarbonylamino group is preferably a substituted orunsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms.Examples of the alkoxycarbonylamino group include a methoxycarbonylaminogroup, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an-octadecyloxycarbonylamino group and an N-methyl-methoxycarbonylaminogroup.

[0083] The aryloxycarbonylamino group is preferably a substituted orunsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms.Examples of the aryloxycarbonylamino group include aphenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group and am-n-octyloxyphenoxycarbonylamino group.

[0084] The sulfamoylamino group is preferably a substituted orunsubstituted sulfamoylamino group having 0 (zero) to 30 carbon atoms.Examples of the sulfamoylamino group include a sulfamoylamino group, anN,N-dimethylaminosulfonylamino group and an N-n-octylaminosulfonylaminogroup.

[0085] The alkyl- or aryl-sulfonylamino group is preferably asubstituted or unsubstituted alkyl sulfonylamino group having 1 to 30carbon atoms, or a substituted or unsubstituted aryl sulfonylamino grouphaving 6 to 30 carbon atoms. Examples of the alkyl- oraryl-sulfonylamino group include a methyl sulfonylamino group, abutylsulfonylamino group, a phenylsulfonylamino group, a2,3,5-trichlorophenylsulfonylamino group and ap-methylphenylsulfonylamino group.

[0086] The alkylthio group is preferably a substituted or unsubstitutedalkylthio group having 1 to 30 carbon atoms. Examples of the alkylthiogroup include a methylthio group, an ethylthio group and an-hexadecylthio group.

[0087] The arylthio group is preferably a substituted or unsubstitutedarylthio group having 6 to 30 carbon atoms. Examples of the arylthiogroup include a phenylthio group, a p-chlorophenylthio group and am-methoxyphenylthio group.

[0088] The heterocyclic thio group is preferably a substituted orunsubstituted heterocyclic thio group having 2 to 30 carbon atoms.Examples of the heterocyclic thio group include a 2-benzothiazolylthiogroup and a 1-phenyltetrazol-5-yl-thio group.

[0089] The sulfamoyl group is preferably a substituted or unsubstitutedsulfamoyl group having 0 (zero) to 30 carbon atoms. Examples of thesulfamoyl group include a N-ethylsulfamoyl group, aN-(3-dodecyloxypropyl)sulfamoyl group, a N,N-dimethylsulfamoyl group, aN-acetylsulfamoyl group, a N-benzoylsulfamoyl group and aN-(N′-phenylcarbamoyl)sulfamoyl group.

[0090] The alkyl- or aryl-sulfinyl group is preferably a substituted orunsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, or asubstituted or unsubstituted arylsulfinyl group having 6 to 30 carbonatoms. Examples of the alkyl- or aryl-sulfinyl group include amethylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group anda p-methylphenylsulfinyl group.

[0091] The alkyl- or aryl-sulfonyl group is preferably a substituted orunsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, asubstituted or unsubstituted arylsulfonyl group having 6 to 30 carbonatoms. Examples of the alkyl- or aryl-sulfonyl group include amethylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group anda p-methylphenylsulfonyl group.

[0092] The acyl group is preferably a formyl group, a substituted orunsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, asubstituted or unsubstituted arylcarbonyl group having 7 to 30 carbonatoms, or a substituted or unsubstituted heterocyclic carbonyl grouphaving 4 to 30 carbon atoms in which the carbonyl group is bonded to acarbon atom in the heterocycle moiety. Examples of the acyl groupinclude an acetyl group, a pivaloyl group, a 2-chloroacetyl group, astearoyl group, a benzoyl group, a p-n-octyloxyphenylcarbonyl group, a2-pyridylcarbonyl group, and a 2-furylcarbonyl group.

[0093] The aryloxycarbonyl group is preferably a substituted orunsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms.Examples of the aryloxycarbonyl group include a phenoxycarbonyl group,an o-chlorophenoxycarbonyl group, a m-nitrophenoxycarbonyl group and ap-t-butylphenoxycarbonyl group.

[0094] The alkoxycarbonyl group is preferably a substituted orunsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. Examplesof the alkoxycarbonyl group include a methoxycarbonyl group, anethoxycarbonyl group, a t-butoxycarbonyl group and an-octadecyloxycarbonyl group.

[0095] The carbamoyl group is preferably a substituted or unsubstitutedcarbamoyl group having 1 to 30 carbon atoms. Examples of the carbamoylgroup include a carbamoyl group, an N-methylcarbamoyl group, anN,N-dimethylcarbamoyl group, an N,N-di-n-octylcarbamoyl group and anN-(methylsulfonyl)carbamoyl group.

[0096] The phosphino group is preferably a substituted or unsubstitutedphosphino group having 2 to 30 carbon atoms. Examples of the phosphinogroup include a dimethylphosphino group, a diphenylphosphino group and amethylphenoxyphosphino group.

[0097] The phosphinyl group is preferably a substituted or unsubstitutedphosphinyl group having 2 to 30 carbon atoms. Examples of the phosphinylgroup include a phosphinyl group, a dioctyloxyphosphinyl group and adiethoxyphosphinyl group.

[0098] The phosphinyloxy group is preferably a substituted orunsubstituted phosphinyloxy group having 2 to 30 carbon atoms. Examplesof the phosphinyloxy group include a diphenoxyphosphinyloxy group and adioctyloxyphosphinyloxy group.

[0099] The phosphinylamino group is preferably a substituted orunsubstituted phosphinylamino group having 2 to 30 carbon atoms.Examples of the phosphinylamino group include a dimethoxyphosphinylaminogroup and a dimethylaminophosphinylamino group.

[0100] The silyl group is preferably a substituted or unsubstitutedsilyl group having 3 to 30 carbon atoms. Examples of the silyl groupinclude a trimethylsilyl group, a t-butyldimethylsilyl group and aphenyldimethylsilyl group.

[0101] Out of the substituents on the aryl group represented by R¹⁰ orR^(10a) listed above, a substituent having a hydrogen atom may besubstituted by any one of the above groups by removing the hydrogenatom. Examples of the substituent include an alkylcarbonylaminosulfonylgroup, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonylgroup and an arylsulfonylaminocarbonyl group. Specific examples of thesubstituent include a methylsulfonylaminocarbonyl group, ap-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl groupand a benzoylaminosulfonyl group.

[0102] A halogen atom, an alkoxy group and an amino group represented byR¹¹ or R¹² have the same meanings as the above-mentioned substituents onthe aryl group. A heterocyclic group represented by R¹¹ or R¹² has thesame meaning as the heterocyclic group represented by Ar in formula (2)or Ar₂ in formula (2-1).

[0103] R¹⁰ and R^(10a) each are preferably an alkyl group. R¹¹ and R¹²each are preferably an amino group.

[0104] Het represents an aromatic heterocyclic group, and similarly inthe above its preferred examples include pyridine, pyrazine, pyrimidine,pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole,thiazole, benzothiazole, isothiazole, benzisothiazole and thiadiazole.Thiadiazole is the most preferred. Each of these may have a substituent,examples of the substituent have the same meanings as the substituent onthe aryl group above.

[0105] The particularly preferred dye is a compound represented by theformula (4).

[0106] One of X and Y is a nitrogen atom, and the other is a —C(—R¹³)═group. Preferably, X is —C(—R¹³)═ and Y is a nitrogen atom. A halogenatom, an alkyl group, an alkylthio group, an alkylsulfonyl group, analkylsulfinyl group, an alkoxycarbonyl group, a carbamoyl group, analkoxy group, an aryl group, an arylthio group, an arylsulfonyl group,an arylsulfinyl group, an aryloxy group and an acylamino group, each ofwhich is represented by R¹³, have the same meanings as theabove-mentioned substituents on the aryl group.

[0107] R¹³ is preferably a hydrogen atom, an alkyl group, an alkylthiogroup or an aryl group.

[0108] Illustrative examples (Exemplified Dyes 1 to 61, and 1B to 25B)of the dye represented by the above formula (1), (2), (3) or (4) aregiven below, but the dye for use in the present invention is not limitedto the following examples. In the following specific examples, Me meansa methyl group, Et means an ethyl group, and Ph means a phenyl group.

Dye R 1 —NHC₂H4COOK 2 —NHC₂H₄SO₃Na 3

4

5

6

7

8

9 —NHC₆H₁₃ 10 —N(C₄H₉)₂

Dye Ar 11

12

13

14

15

16

17

18

Dye R R′ 19 Ph H 20 OC₂H₅ C₂H₅ 21 CH₃ H 22 t-C₄H₉ H 23 t-C₄H₉ —C₂H₄COOHDye 24

Dye R 25 H 26 OCH₃ 27 OH 28 SO₃Na 29 F 30

Dye R¹ R² R³ 31 Cl Cl Cl 32 Cl Cl F 33 Cl —CONHPh Cl

Dye R¹ R² R³ 34 F H H 35 Cl H F

Dye R¹ R² R³ 36 H F F 37 F F H

Dye R 38 3H 39 CH₃ 40 Ph 41 SCH₂COONa 42 SC₂H₅ 43 SC₄H₉-n 44 SCH₂CHMe₂45 SCHMeEt 46 SC₄H₉-t 47 SC₇H₁₅-n 48 SC₂H₄OC₂H₅ 49 SC₂H₄OC₄H₉-n 50SCH₂CF₃

Dye R 51 —NHC₂H₄COOK 52 —NHC₂H₄SO₃Na 53

54

55

56

57 —NHC₆H₁₃-n 58 N(C₄H₉-n)₂ 59

60

61

Dye R R′ 1B —NHC₂H₄SO₃Na H 2B

H 3B —NH—C₄H₉-n H 4B —N(C₄H₉)₂ H 5B —NHC₂H₄SO₃Na —SC₂H₄SO₃Na 6B

H 7B

Ph

Dye Ar R  8B

—NH₂  9B

—OH 10B

—NH₂ 11B

—NH₂

Dye R 12B —CH₃ 13B Ph 14B —OC₂H₅ Dye 15B

Dye R 16B —SCH₂COOCH3 17B —SCH₂COONa 18B —SCH₂CH(CH₃)₂ 19B Ph 20B —SCH₃21B —CH₃

Dye R R′ 22B —SCH₂COONa

23B

24B

25B —SCH₂COOK —N(CH₂COOK)₂

[0109] The dye of the present invention can be synthesized by thefollowing method. As typical examples, the method of synthesizing Dye 2and Dye 5B will be described in detail.

[0110] (Synthetic Example 1)

[0111] 10 g of cyanuric chloride was dissolved in 150 ml of acetone, andwas added thereto 160 ml of an aqueous solution containing 13.6 g oftaurine and 11.5 g of sodium carbonate at 15° C. or less under coolingwith ice, and the resulting mixture was stirred at room temperature for8 hours. 200 ml of acetone was added thereto, and the precipitatedcrystals were separated by filtration, to obtain 22 g of (a).

[0112] 8.1 g of (a) was dissolved in 25 ml of water, 2 g of hydrazinewas added thereto, and the resulting solution was heated at 70° C. for 2hours and then concentrated. The precipitated crystals were separated byfiltration, to obtain 5.7 g of (b).

[0113] A solution of 5.7 g of (b), 1.8 g of pivaloylacetonitrile, 3.6 gof sodium hydrogencarbonate, 30 ml of water and 30 ml of ethanol washeated for 2 hours, and after adding 8 ml of hydrochloric acid thereto,the resulting mixture was further heated for 2 hours. Afterconcentration, the precipitated crystals were separated by filtration,to obtain 5.7 g of (c).

[0114] A mixed solution of 3.4 g of (c), 20 ml of methanol, 13 ml ofacetic acid and 5.5 g of sodium acetate was cooled to 10° C. or less.Separately, using 0.81 g of 5-amino-2,4-thiadiazole, a diazo solutionwas prepared and added to the above mixed solution at 10° C. or less,and the resulting mixture was stirred at room temperature for 2 hours.After the precipitated crystals were separated by filtration, 1 g of Dye2 was obtained by column chromatography using Sephadex (trade name).

λmax 441.9 nm (H₂O), ε: 2.15×10⁴ (dm³/mol cm)

[0115]

[0116] (Synthetic Example 2)

[0117] 10 g of cyanuric chloride was dissolved in 150 ml of acetone, andwas added thereto 160 ml of an aqueous solution containing 6.8 g oftaurine and 6 g of sodium carbonate at 25° C. or less under cooling withice, and the resulting mixture was stirred at room temperature for 8hours and then concentrated, to obtain (al). 20 g of hydrazine was addedthereto at room temperature, and the resulting mixture was stirred at70° C. for 3 hours. After concentration, methanol was added thereto, andthe precipitated crystals were separated by filtration, to obtain 11.3 gof (b1).

[0118] A solution of 11 g of (b1), 9.6 g of pivaloylacetonitrile, 19.2 gof sodium hydrogencarbonate, 60 ml of water and 60 ml of ethanol washeated for 2 hours, and after adding 22 ml of hydrochloric acid thereto,the resulting mixture was further heated for 2 hours. Afterconcentration, the precipitated crystals were separated by filtration,to obtain 9.3 g of (c1).

[0119] A mixed solution of 1.2 g of (c1), 7 ml of methanol, 4.8 ml ofacetic acid and 4.2 g of sodium acetate was cooled to 10° C. or less.Separately, using 1.45 g of 5-amino-3-sulfoethylthio-2,4-thiadiazole, adiazo solution was prepared and added to the above mixed solution at 10°C. or less, and the resulting mixture was stirred at room temperaturefor 2 hours. After the precipitated crystals were separated byfiltration, 1.2 g of Dye 5B was obtained by column chromatography usingSephadex.

λmax 444.5 nm (H₂O), ε: 3.65×10⁴ (dm³/mol cm)

[0120] Other dyes can be synthesized in the similar manner. The maximumabsorption wavelength λmax of typical dyes is shown in Table 1. TABLE 1Dye No. λmax (H₂O)  1 442 nm  2 442 nm  3 444 nm  4 443 nm  5 433 nm  8443 nm 11 443 nm 25 444 nm 38 428 nm 40 440 nm 41 445 nm 42 445 nm 43444 nm 44 445 nm 45 445 nm 47 443 nm 48 444 nm 49 445 nm 50 443 nmλmax/solvent  1B   440 nm/MeOH  2B   441 nm/MeOH  3B   442 nm/MeOH  4B  443 nm/MeOH  5B   445 nm/H₂O  6B   442 nm/H₂O  7B   441 nm/MeOH 16B449.0 nm/MeOH 17B 437.2 nm/H₂O 18B 445.0 nm/MeOH 19B 441.5 nm/MeOH 20B445.0 nm/MeOH 21B 421.8 nm/MeOH

[0121] As use of the dye of the present invention, can be mentionedimage-recording materials for forming an image, particularly a colorimage. Specifically, the use include, in addition to ink-jet-systemrecording materials to be described in detail hereinafter,heat-sensitive recording materials, pressure-sensitive recordingmaterials, recording materials using electrophotographic system,transfer silver halide photosensitive materials, printing inks,recording pens and the like. The use is preferably in ink-jet-systemrecording materials, heat-sensitive recording materials, and recordingmaterials using electrophotographic system, more preferably in ink-jetrecording materials.

[0122] The dye may also be used in color filters for recording andreproducing a color image, which are used in solid image pick-upelements such as CCD and displays such as LCD and PDP, and in dyesolutions for dyeing various fibers.

[0123] The dye of the present invention is used after its physicalproperties such as solubility, dispersibility and thermal mobility areadjusted by a substituent so as to be suitable for its applicationpurpose. The dye of the present invention can be used in a dissolvedstate, an emulsified and dispersed state, or a solid dispersed state,according to a system to be used.

[0124] (Ink)

[0125] The ink of the present invention means an ink comprising at leastone kind of the dye of the present invention. The ink of the presentinvention may contain a medium. When a solvent is used as the medium,the obtained ink is particularly preferable as an ink-jet-recording ink.The ink of the present invention can be prepared by dissolving and/ordispersing the dye of the present invention, in a lipophilic medium oraqueous medium as the medium. An aqueous medium is preferably used. Theink of the present invention includes an ink composition not containingany medium. Other additives may be contained if necessary, within arange not impairing the effect of the present invention. Such otheradditives include, for example, known additives such as a dryinginhibitor (wetting agent), a fade-inhibitor, an emulsion stabilizer, apermeation accelerator, an ultraviolet absorber, an antiseptic, amildewproofing agent, a pH adjuster, a surface-tension modifier, anantifoaming agent, a viscosity modifier, a dispersing agent, adispersion stabilizer, a rust preventive, and a chelating agent. Thesevarious additives are directly added to an ink solution in the case ofan aqueous ink. When an oil-soluble dye is used as a dispersion, theseadditives are generally added to the dispersion after preparation of thedispersion of the dye, but these additives may also be added to an oilphase or water phase during the preparation.

[0126] The above drying inhibitor is preferably used to prevent an inkjet nozzle used in ink jet recording system from being clogged with thedried ink jet recording ink.

[0127] The above drying inhibitor is preferably a water-soluble organicsolvent having a lower vapor pressure than water. Specific examples ofthe drying inhibitor include: polyhydric alcohols typified by ethyleneglycol, propylene glycol, diethylene glycol, polyethylene glycol,thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol,1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, andtrimethylolpropane; lower alkyl ethers of a polyhydric alcohol, such asethylene glycol monomethyl (or ethyl) ether, diethylene glycolmonomethyl (or ethyl) ether, and triethylene glycol monoethyl (or butyl)ether; heterocyclic compounds, such as 2-pyrrolidone,N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, andN-ethylmorpholine; sulfur-containing compounds, such as sulfolane,dimethyl sulfoxide, and 3-sulfolene; polyfunctional compounds, such asdiacetone alcohol, and diethanolamine; and urea derivatives. Out ofthese, polyhydric alcohols such as glycerin and diethylene glycol arepreferred. The above drying inhibitors may be used singly or incombination of two or more of these. The drying inhibitor is preferablycontained in the ink in an amount of 10 to 50 mass %.

[0128] The above permeation accelerator is preferably used for thepurpose of improving permeation of the ink-jet ink into paper. As theabove permeation accelerator, use can be made of an alcohol, such asethanol, isopropanol, butanol, di(tri)ethylene glycol monobutyl ether or1,2-hexanediol, or a nonionic surfactant, such as sodium laurylsulfateor sodium oleate. In general, the permeation accelerator exhibits asatisfactory effect when it is contained in the ink in an amount of 5 to30 mass %. The permeation accelerator is preferably used within therange of an amount to be added that does not cause print through orbleeding (blurring) of printed ink or print.

[0129] The above ultraviolet absorber is used to improve the storabilityof an image. Examples of the ultraviolet absorber that can be usedinclude benzotriazole-based compounds disclosed in JP-A-58-185677,JP-A-61-190537, JP-A-2-782, JP-A-5-197075 and JP-A-9-34057,benzophenone-based compounds disclosed in JP-A-46-2784, JP-A-5-194483and U.S. Pat. No. 3,214,463, cinnamic acid-based compounds disclosed inJP-B-48-30492 (“JP-B” means examined Japanese patent publication),JP-B-56-21141 and JP-A-10-88106, triazine-based compounds disclosed inJP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621 andJP-T-8-501291 (“JP-T” means searched and published International patentapplication), compounds disclosed in Research Disclosure No. 24239, andcompounds which emit fluorescent light by absorbing ultravioletradiation, namely so-called fluorescent brighteners typified bystilbene-based or benzoxazole-based compounds.

[0130] The above fade-inhibitor is used to improve the storability of animage. As the above fade-inhibitor, use can be made of various kinds oforganic or metal complex-based fade-inhibitors. Examples of organicfade-inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols,phenols, anilines, amines, indanes, chromans, alkoxyanilines, andheterocyclic compounds. Examples of such a metal complex include nickelcomplexes and zinc complexes. Specific examples of the fade-inhibitorthat can be used include compounds disclosed in patents cited inparagraphs I to J of Chapter VII of Research Disclosure No. 17643,Research Disclosure No. 15162, left column in page 650 of ResearchDisclosure No. 18716, page 527 of Research Disclosure No. 36544, page872 of Research Disclosure No. 307105, and Research Disclosure No.15162; and compounds included in the formulas of typical compounds andcompound examples disclosed in pages 127 to 137 of JP-A-62-215272.

[0131] Examples of the mildewproofing agent include sodiumdihydroacetate, sodium benzoate, sodium pyridinethion-1-oxide,p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one, and saltsthereof. The mildewproofing agent is preferably used in the ink in anamount of 0.02 to 1.00 mass %. As for the details of these agents, refercan be made, for example, to “Bohkin Bohkabizai Jiten” (Encyclopedia ofAntifungal Agents and Mildewproofing Agents) (edited by the encyclopediaediting committee of the Japan Antifungal and Mildewproofing AgentAssociation).

[0132] Examples of the above rust preventive include acidic sulfurousacid salts, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexyl ammoniumnitrite and benzotriazole. The rust preventive is preferably used in theink in an amount of 0.02 to 5.00 mass %.

[0133] As the above pH adjuster, use can be made of the aboveneutralizer (organic base, inorganic alkali). The above pH adjuster ispreferably added to ensure that the pH of the ink-jet ink becomepreferably 6 to 10, more preferably 7 to 10, for the purpose ofimproving the shelf stability of the ink-jet ink.

[0134] As the above surface-tension modifier, mention can be made of anonionic, cationic or anionic surfactant. The surface tension of theink-jet ink of the present invention is preferably 20 to 60 mN/m, morepreferably 25 to 45 mN/m. The viscosity of the ink-jet ink of thepresent invention is preferably 30 mpa·s or less, more preferably 20mPa·s or less. Examples of the surfactant include: anionic surfactants,such as fatty acid salts, alkyl sulfuric acid ester salts, alkyl benzenesulfonic acid salts, alkyl naphthalene sulfonic acid salts, dialkylsulfosuccinic acid salts, alkyl phosphoric acid ester salts, naphthalenesulfonic acid formalin condensates, and polyoxyethylene alkyl sulfuricacid ester salts; and nonionic surfactants, such as polyoxyethylenealkyl ethers, polyoxyethylene alkylallyl ethers, polyoxyethylene fattyacid esters, sorbitan fatty acid esters, polyxoyethylene sorbitan fattyacid esters, polyoxyethylene alkylamines, glycerin fatty acid esters,and oxyethylene oxypropylene block copolymers. SURFYNOLS (trade name,manufactured by Air Products & Chemicals, Inc.) which is anacetylene-based polyoxethyleneoxide surfactant can also be preferablyused. An amine oxide-type amphoteric surfactant, such asN,N-dimethyl-N-alkylamine oxide, is also preferred. Further, surfactantsenumerated in pages (37) to (38) of JP-A-59-157,636, and ResearchDisclosure No. 308119 (1989) may also be used.

[0135] As the above antifoaming agent, use can be made, if necessary, ofa fluorine-containing or silicone-based compound, or a chelating agenttypified by EDTA.

[0136] In order to disperse the compound of the present invention in anaqueous medium, it is preferred that coloring fine-particles containingthe dye and an oil-soluble polymer be dispersed in an aqueous medium, asdisclosed in JP-A-11-286637, and Japanese Patent Application Nos.2000-78491, 2000-80259 and 2000-62370; or that the dye of the presentinvention which is dissolved in a high-boiling organic solvent bedispersed in an aqueous medium, as disclosed in Japanese PatentApplication Nos. 2000-78454, 2000-78491, 2000-203856 and 2000-203857. Asfor the specific method of dispersing the dye of the present inventionin an aqueous medium, and the oil-soluble polymer, high-boiling organicsolvent and additives to be used in the methods, and the amounts to beused thereof, those disclosed by the above patents are preferablyadopted. Alternatively, the above azo dye in the solid state may bedirectly dispersed in the form of fine particles. At the time ofdispersing, a dispersing agent or a surfactant may be used. Examples ofthe dispersing apparatus that can be used include a simple stirrer orimpeller, an in-line mixer, a mill (e.g., a colloid mill, a ball mill, asand mill, an attritor, a roller mill, or an agitator mill), anultrasonic disperser, and a high-pressure emulsifying disperser(high-pressure homogenizer: gorille homogenizer, micro-fluidizer, DeBEE2000, etc. as commercially available apparatuses). In addition to theabove patent publications, the details of the methods of preparing theink-jet recording ink are described in JP-A-5-148436, JP-A-5-295312,JP-A-7-97541, JP-A-7-82515, JP-A-7-118584, JP-A-11-286637, and JapanesePatent Application No. 2000-87539. These methods can also be utilized inthe preparation of the ink-jet-recording ink of the present invention.

[0137] The aqueous medium described above can be a mixture composed ofwater as a main component and a water-miscible organic solvent as anoptional component. Examples of the water-miscible organic solventinclude alcohols (e.g., methanol, ethanol, propanol, isopropanol,butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol,cyclohexanol and benzylalcohol), polyhydric alcohols (e.g., ethyleneglycol, diethylene glycol, triethylene glycol, polyethylene glycol,propylene glycol, dipropylene glycol, polypropylene glycol, butyleneglycol, hexanediol, pentanediol, glycerin, hexanetriol, andthiodiglycol), glycol derivatives (e.g., ethylene glycol monomethylether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,diethylene glycol monomethyl ether, diethylene glycol monobutyl ether,propylene glycol monomethyl ether, propylene glycol monobutyl ether,dipropylene glycol monomethyl ether, triethylene glycol monomethylether, ethylene glycol diacetate, ethylene glycol monomethyl etheracetate, triethylene glycol monomethyl ether, triethylene glycolmonoethyl ether, and ethylene glycol monophenyl ether), amines (e.g.,ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine,N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine,diethylenetriamine, triethylenetetramine, polyethyleneimine, andtetramethylpropylenediamine), and other polar solvents (e.g., formamide,N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide,sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone,2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, andacetone). These water-miscible organic solvents may be used incombination of two or more of these.

[0138] It is preferable that the compound of the present invention in anamount of 0.2 parts by mass or more and 10 parts by mass or less iscontained, in 100 parts by mass of the ink of the present invention. Theink of the present invention may contain another dye together with thecompound of the present invention. In the case where two kinds or moreof dyes are used in combination, it is preferable that the total contentof the dye compounds falls within the above-described range.

[0139] The ink of the present invention can be used not only for theformation of a single-color image but also for the formation of afull-color image. For the formation of a full-color image, amagenta-color tone ink, a cyan-color tone ink, and a yellow-color toneink can be used. In addition, for the adjustment of colors, ablack-color tone ink may also be used.

[0140] Further, the ink of the present invention may contain a yellowdye besides the dye of the present invention. Any yellow dye may beused. Examples of the yellow dye include: aryl or heterylazo dyeshaving, for example, any of phenols, naphthols, anilines, heterocycliccompounds such as pyrazolone or pyridone, or open-chain active methylenecompounds, as a coupling component (to be referred to as “couplercomponent” hereinafter); azomethine dyes having, for example, anopen-chain active methylene compound as a coupler component; methinedyes, such as benzylidene dyes and monomethine oxonol dyes;quinone-based dyes, such as naphthoquinone dyes and anthraquinone dyes;and other dyes, including quinophthalone dyes, nitro/nitroso dyes,acridine dyes and acridinone dyes.

[0141] Any magenta dye may be used. Examples of the magenta dye include:aryl or heterylazo dyes having, for examples, any of phenols, naphtholsor anilines, as a coupler component; azomethine dyes having, forexample, any of pyrazolones or pyrazolotriazoles, as a couplercomponent; methine dyes, such as arylidene dyes, styryl dyes,merocyanine dyes, cyanine dyes or oxonol dyes; carbonium dyes, such asdiphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinonedyes, such as naphthoquinone, anthraquinone and anthrapyridone; andcondensation polycyclic dyes, such as dioxazine dyes.

[0142] Any cyan dye may be used. Examples of the cyan dye include: arylor heterylazo dyes having, for example, any of phenols, naphthols oranilines, as a coupler component; azomethine dyes having, for example,any of phenols, naphthols or heterocyclic compounds such aspyrrolotriazole, as a coupler component; polymethine dyes, such ascyanine dyes, oxonol dyes and merocyanine dyes; carbonium dyes, such asdiphenylmethane dyes, triphenylmethane dyes and xanthene dyes;phthalocyanine dyes; anthraquinone dyes; and indigo/thioindigo dyes.

[0143] The above dyes may assume a yellow, magenta or cyan color onlyafter a part of a chromophore therein is dissociated. In this case, thecounter cation may be an inorganic cation such as alkali metal orammonium, an organic cation such as pyridinium or a quaternary ammoniumsalt, or a polymer cation having any one of these in its partialstructure.

[0144] Examples of the black dye that can be used include disazo dyes,trisazo dyes, tetraazo dyes, and carbon black dispersion.

[0145] (Ink-Jet-Recording Method)

[0146] The ink-jet recording method of the present invention comprisesapplying an energy to the ink, to form an image on a knownimage-receiving material. Examples of the image-receiving materialinclude plain paper, resin-coated paper; paper exclusively for ink-jetrecording described, for example, in JP-A-8-169172, JP-A-8-27693,JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783,JP-A-10-153989, JP-A-10-217473, JP-A-10-235995, JP-A-10-337947,JP-A-10-217597, and JP-A-10-337947; films, paper for bothelectrophotography and ink-jet recording, fabrics, glass, metals, andceramics.

[0147] A polymer latex compound may be additionally used, to providesurface gloss or water resistance or improve weatherability, when animage is formed. The time for adding a latex compound to an imagereceiving material may be before or after the addition of a colorant orsimultaneous with the addition of a colorant. Therefore, the site foradding the latex compound may be in image receiving paper or ink.Alternatively, the polymer latex compound may be used alone as a liquid.Specifically, methods disclosed in Japanese Patent Application Nos.2000-363090, 2000-315231, 2000-354380, 2000-343944, 2000-268952,2000-299465 and 20000-297365, can be preferably used.

[0148] The recording paper and recording films, which are to be used forink-jet printing using the ink of the present invention, are describedbelow. The supports for use in the recording paper and recording filmsmay be those produced by such an apparatus as a long-screen papermachine and a circular-screen paper machine, and from pulps such aschemical pulps, e.g., LBKP and NBKP, mechanical pulps, e.g., GP, PGW,RMP, TMP, CTMP, CMP, and CGP, waste paper pulp, e.g., DIP, and, ifnecessary, additives such as conventionally known pigments, binders,sizing agents, fixing agents, cationic agents, and fortifiers for paperstrength may be contained. Besides these materials, the support may be asynthetic paper or a plastic film sheet. The thickness of the support ispreferably 10 to 250 μm, and the weight is preferably 10 to 250 g/m². Anink-receiving layer and a back coat layer may be formed directly on thesupport. Alternatively, an ink-receiving layer and a back coat layer maybe provided after a size press or anchor coat layer, which is made fromstarch, polyvinyl alcohol, or the like, is provided on the support. Thesupport may be flattened by means of a calender such as a machinecalender, a TG calender, or a soft calender. The support that ispreferably used in the present invention is a plastic film or a paperwhose both surfaces are laminated with a polyolefin (e.g., polyethylene,polystyrene, polyethylene terephthalate, polybutene, or a copolymerthereof). It is preferable that the polyolefin contains a white pigment(e.g., titanium oxide, zinc oxide) or a dye for giving tinge (e.g.,cobalt blue, ultramarine blue, neodymium oxide).

[0149] The ink-receiving layer provided on the support generallycontains a pigment and an aqueous binder. The pigment is preferably awhite pigment. Examples of the white pigment include white inorganicpigments, such as calcium carbonate, kaolin, talc, clay, diatomaceousearth, synthetic amorphous silica, aluminum silicate, magnesiumsilicate, calcium silicate, aluminum hydroxide, alumina, lithopone,zeolite, barium sulfate, calcium sulfate, titanium dioxide, zincsulfide, and zinc carbonate; and organic pigments, such as astyrene-based pigment, an acryl-based pigment, a urea resin, and amelamine resin. The white pigment to be incorporated in theink-receiving layer is preferably a porous inorganic pigment. Syntheticamorphous silica or the like having a high proportion of porous area isparticularly preferable. The synthetic amorphous silica that can be usedmay be silicic acid anhydride produced by a dry process or hydroussilicic acid produced by a wet process. The use of hydrous silicic acidis particularly preferable.

[0150] Examples of the aqueous binder to be incorporated in theink-receiving layer include water-soluble polymers, such as polyvinylalcohol, silanol-modified polyvinyl alcohol, starch, cationized starch,casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose,polyvinylpyrrolidone, polyalkylene oxide, and derivatives ofpolyalkylene oxide; and water-dispersible polymers, such as astyrene/butadiene latex and an acrylic emulsion. These aqueous bindersmay be used singly or in combination of two or more. Among these aqueousbinders, polyvinyl alcohol and silanol-modified polyvinyl alcohol arepreferably used in the present invention, from the standpoint ofadhesion to the pigment and peel resistance of the ink-receiving layer.

[0151] In addition to the pigment and aqueous binder, the ink-receivinglayer may contain a mordant, a water-proofing agent, a lightfastnessenhancer, a surfactant, and other additives.

[0152] It is preferable that the mordant to be incorporated in theink-receiving layer is immobilized. Accordingly, a polymeric mordant ispreferably used.

[0153] The polymeric mordants are described in JP-A-48-28325,JP-A-54-74430, JP-A-54-124726, JP-A-55-22766, JP-A-55-142339,JP-A-60-23850, JP-A-60-23851, JP-A-60-23852, JP-A-60-23853,JP-A-60-57836, JP-A-60-60643, JP-A-60-118834, JP-A-60-122940,JP-A-60-122941, JP-A-60-122942, JP-A-60-235134, and JP-A-1-161236, andU.S. Pat. Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124,4,124,386, 4,193,800, 4,273,853, 4,282,305, and 4,450,224. Theimage-receiving materials containing the polymeric mordants described inJP-A-1-161236, pp.212 to 215, are particularly preferable. The use ofthe polymeric mordant described in this patent publication makes itpossible to obtain an image having excellent quality and to improve thelightfastness of the image.

[0154] The waterproofing agent is effective in increasing the waterresistance of an image. The waterproofing agent is particularlypreferably a cationic resin. Examples of the cationic resin includepolyamide/polyamine/epichlorohydrin, polyethylene imine, polyaminesulfone, dimethyldiallylammonium chloride polymers, cationicpolyacrylamide, and colloidal silica. Among these cationic resins,polyamide/polyamine/epichlorohydrin is particularly preferable. Thecontent of the cationic resin is preferably 1 to 15% by mass,particularly preferably 3 to 10% by mass, to the total solid componentsof the ink-receiving layer.

[0155] Examples of the lightfastness enhancer include zinc sulfate, zincoxide, hindered amine-based antioxidants, and benzotriazole-basedultraviolet light absorbers such as benzophenone. Among thesesubstances, zinc sulfate is particularly preferable.

[0156] The surfactant functions as a coating aid, apeelability-improving agent, a slidability-improving agent, or anantistatic agent.

[0157] The surfactants are described in JP-A-62-173463 andJP-A-62-183457. An organofluorine compound may be used in place of thesurfactant. Preferably, the organofluorine compound is hydrophobic.Examples of the organofluorine compound include a fluorine-containingsurfactant, an oily fluorine-containing compound (e.g., fluorine-basedoil), and a solid fluorine-containing compound resin (e.g.,tetrafluoroethylene resin). The organofluorine compounds are describedin JP-B-57-9053 (columns 8 to 17), and JP-A-61-20994 and JP-A-62-135826.Examples of other additives which may be added to the ink-receivinglayer include a pigment dispersant, a thickener, a defoaming agent, adye, a fluorescent brightener, an antiseptic, a pH controlling agent, amatting agent, a film hardener. The ink-receiving layer may have asingle-layer construction or a double-layer construction

[0158] The recording paper or recording film may have a back coat layer.This layer may contain a white pigment, an aqueous binder, and othercomponents. Examples of the white pigment to be incorporated in the backcoat layer include white inorganic pigments, such as light calciumcarbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate,barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinccarbonate, titanium white, aluminum silicate, diatomaceous earth,calcium silicate, magnesium silicate, synthetic amorphous silica,colloidal silica, colloidal alumina, quasi-boehmite, aluminum hydroxide,alumina, lithopone, zeolite, hydrated halloysite, magnesium carbonate,and magnesium hydroxide; and organic pigments, such as styrene-basedplastic pigments, acryl-based plastic pigments, polyethylenes,microcapsules, urea resins, and melamine resins.

[0159] Examples of the aqueous binder to be incorporated in the backcoat layer include water-soluble polymers, such as a styrene/maleic acidsalt copolymer, a styrene/acrylic acid salt copolymer, polyvinylalcohol, silanol-modified polyvinyl alcohol, starch, cationized starch,casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, andpolyvinylpyrrolidone; and water-dispersible polymers, such as astyrene/butadiene latex and an acrylic emulsion. Other components whichmay be incorporated in the back coat layer include a defoaming agent, afoaming inhibitor, a dye, a fluorescent brightener, an antiseptic, awater-proofing agent.

[0160] The layers constituting the ink-jet recording paper or recordingfilm (including a back coat layer) may contain a polymer latex. Thepolymer latex is used for improvement of film physical properties, suchas dimension stabilization, curling prevention, adhesion prevention, andprevention of film cracking. The polymer latices are described inJP-A-62-245258, JP-A-62-131668, and JP-A-62-110066. The incorporation ofa polymer latex having a low glass transition temperature (i.e., 40° C.or below) in the layer containing a mordant, can prevent cracking andcurling of the layer. The incorporation of a polymer latex having a highglass transition temperature in the back coat layer can also preventcurling of the layer.

[0161] The ink-jet recording methods using the ink of the presentinvention are not particularly limited, and any of known methods can beused. Examples of the method include a charge-controlling method, inwhich ink is ejected (discharged) by use of electrostatic attraction; adrop-on-demand method (pressure pulse method), in which vibratorypressure of a piezoelectric element is used; an acoustic ink-jet method,in which electric signals are converted into acoustic beams, and the inkis irradiated with the acoustic beams so that the ink is ejected by useof the radiation pressure; and a thermal ink-jet method, in whichbubbles are formed by heating the ink, and the pressure thus occurred isused for discharging the ink. Other types of the ink-jet recordingmethod include a method, in which many droplets, each made up of a smallvolume of a so-called photo-ink having a low concentration, are ejected;a method in which image quality is improved by use of plural kinds ofink each having substantially the same color hue but a differentconcentration; and a method in which colorless transparent ink is used.

[0162] (Color Toner)

[0163] Any kinds of binders which are commonly used, may be used as acolor toner binder resin for introducing the dye of the presentinvention. Examples of the binder resin include styrene-based resins,acrylic resins, styrene/acrylic resins and polyester resins. Thecompound of the present invention is contained in an amount to begenerally used, without particular limitation.

[0164] Inorganic fine-particles and organic fine-particles may beexternally added to the toner, for the purposes of improving fluidityand controlling antistatic properties. Silica fine-particles and titaniafine-grains whose surfaces are treated, for example, with a couplingagent containing an alkyl group are preferably used. Preferably, thesefine-particles have a number average primary particle diameter of 10 to500 nm and are contained in the toner in an amount of 0.1 to 20 mass %.

[0165] Any release agents which have been conventionally used may beused in the present invention. Specific examples of the release agentinclude olefins, such as low-molecular-weight polypropylenes,low-molecular-weight polyethylenes, and ethylene/propylene copolymers;microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. Therelease agent is preferably added to the toner in an amount of 1 to 5mass %.

[0166] The charge-control agent may be added if necessary. It ispreferably to use an achromatic charge control agent, from the viewpointof color-forming property. Examples of the charge control agent includethose having a quaternary ammonium salt structure or calyx allenestructure.

[0167] The carrier to be used may be either an uncoated carrier composedof only magnetic material particles such as iron or ferrite, or aresin-coated carrier obtained by coating the surface of a magneticmaterial particle with a resin or the like. The average particlediameter of this carrier is preferably 30 to 150 μm in terms of volumeaverage particle diameter.

[0168] The method of forming an image, in which the toner according tothe present invention is used, is not particularly limited. Examples ofthe method include a method in which color images are repeatedly formedon a photosensitive material and then transferred, to form an image; anda method in which images formed on a photosensitive material aretransferred to an intermediate transfer material and the likesequentially, and then a color image formed on the intermediate transfermaterial is transferred to an image-forming member such as paper, toform a color image.

[0169] (Heat-Sensitive Transfer Material)

[0170] The heat-sensitive recording material comprises: an ink sheetprepared by applying the dye of the present invention onto a base,together with a binder; and an image-receiving sheet for fixing the dyetransferred corresponding to thermal energy given from a thermal head inresponse to an image recording signal. The ink sheet can be formed, bydissolving the compound of the present invention in a solvent togetherwith a binder or dispersing the compound in a solvent in the form offine particles, to prepare an ink solution, and then applying the ink tothe base, and optionally drying the resultant base. The compound of thepresent invention is contained in a commonly used amount, withoutparticular restriction.

[0171] As the preferred binder resin, ink solvent, base, andimage-receiving sheet, each of which can be used, those disclosed inJP-A-7-137466 can be preferably used.

[0172] In order to use the above heat-sensitive recording material as aheat-sensitive recording material capable of recording a full-colorimage, it is preferred that a cyan ink sheet containing a thermallydiffusible cyan dye which can form a cyan image, a magenta ink sheetcontaining a thermally diffusible magenta dye which can form a magentaimage, and a yellow ink sheet containing a thermally diffusible yellowdye which can form a yellow image be formed on a base by applyingsequentially. In addition to the above ink sheets, an ink sheetcontaining a black-image-forming substance may be further formed asrequired.

[0173] (Color Filter)

[0174] As the method of forming a color filter, can be mentioned amethod in which a pattern is formed with a photoresist, and then dyed;and a method in which a pattern is formed with a photoresist containinga dye, as disclosed in JP-A-4-163552, JP-A-4-128703 and JP-A-4-175753.To introduce the dye of the present invention into a color filter, anyone of the above methods may be used. Examples of preferred meansincludes, as disclosed in JP-A-4-175753 and JP-A-6-35182, a positiveresist composition containing a thermosetting resin, a quinonediazidocompound, a crosslinking agent, a dye and a solvent; and a method offorming a color filter which comprises: applying the composition onto abase, subjecting the applied base exposure to light through a mask,subjected the exposed portion to development, to form a positive resistpattern, exposing the entire positive resist pattern to light, andcuring the exposed positive resist pattern. Further, a color filter ofRGB primary colors or Y. M. C. complementary colors can be obtained, byforming a black matrix in accordance in a usual manner.

[0175] As for the thermosetting resin, quinonediazido compound,crosslinking agent and solvent to be used, and the amounts to be usedthereof, those disclosed in the above patent publications can bepreferably used. The compound of the present invention is contained inan amount to be generally used, without particular restriction.

[0176] According to the present invention, can be provided:

[0177] 1) a novel compound, which can be preferably used as a dye, andwhich has absorption characteristics with excellent color reproductionas a dye for three primary colors, and which has satisfactorycolorfastness against light, heat, humidity, and an active gas presentin the environment;

[0178] 2) an ink for ink jet printing, to give a colored image orcolored material having excellent hue and colorfastness, an ink sheetfor heat-sensitive recording materials, a color toner forelectrophotography, a color filter for use in displays such as LCD andPDP and image pick-up elements such as CCD, and various coloringcompositions such as a dye solution for dying various fibers;

[0179] 3) in particular, an ink (e.g. an ink for ink jet recording), andan ink-jet-recording method, which can form an image having a good huedue to use of the above dye and having high fastness under the variousservice conditions or environmental conditions, for example, againstlight, humidity and heat, and an active gas present in the environment,particularly an ozone gas; and

[0180] 4) a novel dye derivative having a specific structure which canbe a useful organic compound or intermediate thereof for use inindustrial, agricultural, medical or scientific fields.

[0181] The present invention will be described in more detail based onthe following examples, but the present invention is not limitedthereto.

EXAMPLES Example 1

[0182] Deionized water was added to the following components, to make 1liter in volume. Then, the resulting mixture was stirred for 1 hourunder heating at 30 to 40° C. Thereafter, pH of the mixture was adjustedto 9 with 10 mol/l of KOH, and the obtained solution was vacuum filteredwith a microfilter having an average opening diameter of 0.25 μm, toprepare a yellow ink solution. (Composition of ink solution A1) Yellowdye 2 of this invention  8.9 g Diethylene glycol   20 g Glycerin  120 gDiethylene glycol monobutyl ehter  230 g 2-Pyrrolidone   80 gTriethanolamine 17.9 g Benzotriazole 0.06 g SURFYNOL TG  8.5 g (tradename, manufactured by Air Products Co.) PROXEL XL2  1.8 g (trade name,manufactured by ICI Co., Ltd.)

[0183] Ink solutions B1, C1, and A2 to C2 were prepared in the samemanner as in the preparation of the ink solution A1, except that the dyewas changed as shown in the following Table 2.

[0184] Separately, ink solutions 101 and 102 were prepared as inksolutions for comparison, using the following dye for comparison A or B,as shown in Table 2, respectively.

[0185] When a different dye was used, such a dye was contained in anequimolar amount to be contained, to the ink solution A1.

[0186] (Image Recording and Evaluation)

[0187] The following evaluations were carried out, with respect to theink-jet inks of Examples (ink solutions A1 to C1 and A2 to C2) andComparative Examples (ink solutions 101 and 102). The results are shownin Table 2.

[0188] In Table 2, “color tone”, “paper dependence”, “water resistance”,“light resistance” and “ozone gas resistance” were evaluated after animage was recorded on a photo glossy paper (“Gloss” PM photo paperproduced by SEIKO EPSON CORPORATION, trade name: KA420PSK, EPSON) withan ink jet printer (manufactured by SEIKO EPSON CORPORATION, trade name:PM-700C), filling a cartridge with any one of the inks for ink jet.

[0189] <Color Tone>

[0190] The color tone was evaluated with the naked eye based on threegrades of “A” (excellent), “B” (good) and “C” (poor). The value λmax ofthe reflection spectrum of the PM photo paper is also shown.

[0191] <Paper Dependence>

[0192] The above photo glossy paper or PPC plain paper was printed,setting the printing density of the above printer to “toner savingmode”. With respect to color tone, comparison was made between the imageformed on the photo glossy paper and the image formed on PPC plainpaper. If the difference between the two images was small, it was gradedas “A” (good), whereas, if the difference between the two images waslarge, it was graded as “B” (poor). In this way, the difference wasevaluated according to the two grades.

[0193] <Water Resistance>

[0194] After the image was formed on the photo glossy paper, the paperwas dried for one hour at room temperature. After that, the paper wasimmersed in deionized water for 10 seconds and thereafter left to drynaturally at room temperature. The blur on the paper was inspected. Theblur was expressed by the following three ratings: “A”, less blur; “B”,intermediate extent of blur; and “C”, significant blur.

[0195] <Light Resistance>

[0196] The photo glossy paper having an image formed thereon wasirradiated with xenon light (85,000 lx) by means of a weather-o-meter(Atlas C. I65, trade name, manufactured by Atlas) for 7 days. Before andafter the xenon irradiation, the image densities were measured using areflection densitometer (X-Rite 310TR, trade name, manufactured byX-Rite) and the values obtained were used for the calculation of the dyeretention (or retained) rate [(image density after xenonirradiation)/(image density before xenon irradiation)×100%]. Themeasurement was made at three points of reflection densities, i.e., 1,1.5, and 2.0 in terms of the image density before the irradiation.

[0197] The dye retention rate was expressed by the following threeratings: “A” indicates that the dye retention rate was 70% or more atall of the densities; “B” indicates that the dye retention rate was lessthan 70% at one or two of the densities; and “C” indicates that the dyeretention rate was less than 70% at all of the densities.

[0198] <Ozone Resistance>

[0199] The photo glossy paper having an image formed thereon was placedin a box provided in dark location, at room temperatre, in which theozone gas concentration was set to 0.5±0.1 ppm, for 7 days. Before andafter the exposure to the ozone gas, the image densities were measuredusing a reflection densitometer (X-Rite 310TR), and the ozone gasresistance was evaluated based on the dye retention rate [(image densityafter exposure to ozone)/(image density before exposure to ozone)×100%].The measurement was made at three points of reflection densities, i.e.,1, 1.5, and 2.0 in terms of the image density before the exposure toozone. The ozone gas concentration inside the box was set by means of anozone gas monitor (Model: OZG-EM-01) manufactured by APPLICS.

[0200] The ozone gas resistance was expressed by the following threeratings: “A” indicates that the dye retention rate was 70% or more atall of the densities; “B” indicates that the dye retention rate was lessthan 70% at one or two of the densities; and “C” indicates that the dyeretention rate was less than 70% at all of the densities. TABLE 2 ColorPaper Water Light Ozone Sample tone depend- resist- resist- resist- No.Dye (λmax) ence ance ance ance A1 2 A A A A A (452 nm) B1 3 A A A A A(455 nm) C1 4 A A A A A (453 nm) A2 5B A A A A A (460 nm) B2 2B A A A AA (452 nm) C2 6B A A A A A (451 nm) 101 Dye A for B B A A C Comparison(423 nm) 102 Dye B for C B B C C Comparison (471 nm) Dye for comparisonA

Dye for comparison B

[0201] As can be seen from the results in Table 2, the ink-jet ink ofthe present invention exhibited excellent color tone, little dependenceon paper, and excellent water resistance, lightfastness and resistanceto ozone. In particular, it is apparent that the ink of the presentinvention was excellent in image storability, such as light resistanceand ozone resistance. The ink of the present invention was alsoexcellent in moist heat resistance.

Example 2

[0202] An image was printed on an ink jet paper photo glossy paper EX(trade name) manufactured by Fuji Photo Film Co., Ltd., using the sameprinter as in Example 1 using the same cartridge as in Example 1, tocarry out the same evaluations as in Example 1. The similar results asin Example 1 were obtained.

Example 3

[0203] Each ink solution prepared in Example 1 was loaded into acartridge of an ink-jet printer BJ-F850 (trade name, manufactured byCANON Inc.). Using the printer and a photo glossy paper GP-301 (tradename) manufactured by CANON Inc., images were printed. The printsunderwent the same evaluations as in Example 1, and the similar resultsas in Example 1 were obtained.

Example 4

[0204] (Preparation of Ink Solution D1)

[0205] 3.75 g of Dye 9 of the present invention, and 7.04 g of sodiumdioctylsulfosuccinate were dissolved in 4.22 g of a high-boiling-pointorganic solvent (S-2) shown below, 5.63 g of a high-boiling-pointorganic solvent (S-11) shown below and 50 mL of ethyl acetate at 70° C.After that, to the resulting solution, was added 500 mL of deionizedwater, while stirring by means of a magnetic stirrer, to prepare anoil-in-water-type coarse dispersion. The coarse dispersion thus obtainedwas passed through a micro-fluidizer (manufactured by MICROFLUIDEX INC.)five times under a pressure of 600 bar, to obtain an emulsion havingfiner particles. Then, the resulting emulsion underwent asolvent-removing treatment by means of a rotary evaporator until thesmell of ethyl acetate was lost. In this way, a fine emulsion of ahydrophobic dye was obtained. Then, 140 g of diethylene glycol, 50 g ofglycerin, 7 g of SURFYNOL 465 (trade name, manufactured by Air Products& Chemicals Inc.), and 900 mL of deionized water were added to the fineemulsion, to prepare Ink solution D1.

[0206] (Preparation of Ink Solution E1, D2, E2)

[0207] Ink solutions E1, D2 and E2, and ink solution for comparison 103were prepared in the same manner as in the preparation of Ink solutionD1, except that Dye 9 was replaced by any of the dyes in an equimolaramount as shown in the following Table 3.

[0208] (Image Recording and Evaluation)

[0209] The ink solutions D1, E1, D2 and E2, and ink solution forcomparison 103 were underwent the following evaluations. The results areshown in Table 3.

[0210] In Table 3, “color tone (λmax)”, “paper dependence”, “waterresistance”, “light resistance” and “ozone gas resistance” have the samemeanings under the test conditions and evaluation grades, as describedin Example 1, respectively. TABLE 3 Color Paper Water Light Ozone Sampletone depend- resist- resist- resist- No. Dye (λmax) ence ance ance anceD1 9 A A A A A (450 nm) E1 10 A A A A A (452 nm) D2 3B A A A A A (451nm) E2 4B A A A A A (452 nm) 103 Dye C for B B B C C Comparison (430 nm)Dye for comparison C

[0211] As is apparent from the results in Table 3, the ink of thepresent invention, for example, as an ink for ink jet exhibitedexcellent color-forming property and color tone, little dependence onpaper, and excellent water resistance, light resistance and ozoneresistance.

Example 5

[0212] An image was printed on an ink jet paper photo glossy paper EX(trade name) manufactured by Fuji Photo Film Co., Ltd., using the sameprinter as in Example 4 using the same cartridge as in Example 4, tocarry out the same evaluations as in Example 4. The similar results asin Example 4 were obtained.

Example 6

[0213] Each ink solution prepared in Example 4 was loaded into acartridge of an ink-jet printer BJ-F850 (trade name, manufactured byCANON Inc.). Using the printer and a photo glossy paper GP-301 (tradename) manufactured by CANON Inc., images were printed. The printsunderwent the same evaluations as in Example 4, and the similar resultsas in Example 4 were obtained.

Example 7

[0214] 3 parts by mass of Dye 9 of the present invention and 100 partsby mass of a toner resin (a styrene/acrylate copolymer; trade name:Himer TB-1000F (manufactured by Sanyo Chemical Industries, Ltd.), weremixed together and ground by a ball mill, and then the resultant mixturewas fusion-mixed together by heating at 150° C., cooled, roughly groundby a hammer mill, and then finely ground by an air jet fine grinder. Theobtained fine particles were classified to select particles as fine as 1to 20 μm for use as a toner. Then, 10 parts by mass of the toner and 900parts by mass of carrier iron powders (trade name: EFV250/400,manufactured by Nippon Teppun Co., Ltd.) were uniformly mixed together,to prepare a developing agent. Each sample was prepared in the samemanner as above, except that 3 parts by mass of a dye or 6 parts by massof a pigment was used as a colorant, as shown in Table 4. Reproduction(copying) was carried out by a dry PPC electrophotographic copier (tradename: NP-5000, manufactured by Canon Inc.) using any of these developingagents.

[0215] Evaluation tests were carried out in accordance with thefollowing methods: by forming a reflection image (an image on a paper)and a transmission image (an OHP image), on a paper and an OHP,respectively, by the above-described image-forming method with adeveloping agent, using the color toner of the present invention. Thedeposition amount of the toner was within the range of 0.7±0.05 (mg/cm²)in evaluation.

[0216] The hue and lightfastness of the thus-obtained images wereevaluated. The hue was evaluated with the naked eye based on threegrades: “excellent”, “good” and “poor”. The evaluation results are shownin Table 4 below. In Table 4, “◯” represents excellent hue, “Δ”represents good hue, and “X” represents poor hue. As for lightfastness,after the density Ci of an image right after recording was measured, theimage was exposed to xenon light (85,000 lx) for 5 days using a weathermeter (Atlas C. 165), and the density Cf of the image was measuredagain, to calculate the dye retention rate ({(Ci−Cf)/Ci}×100%) from thedifference in image density before and after exposure to xenon light,for evaluating. The density of the image was measured using a reflectiondensitometer (X-Rite310TR). The evaluation results are shown in Table 4below. In Table 4 below, “◯” indicates a dye residual rate of 90% ormore, “Δ” indicates a dye residual rate of less than 90% but not lessthan 80%, and “X” indicates a dye residual rate of less than 80%.

[0217] The transparency of the OHP images was evaluated by the followingmethod. The visible light transmittance of an image was measured, usingthat of an OHP sheet which did not carry a toner as a reference by using“330-Type Autographic Spectrophotometer”, trade name, manufactured byHitachi Ltd., to obtain a spectral transmission factor at 650 nm as anindex of the transparency of the OHP image. As evaluation grades, “◯”indicates a spectral transmission factor of 80% or more, “Δ” indicates aspectral transmission factor of more than 70% but less than 80%, and “X”indicates a spectral transmission factor of 70% or less. The results ofthe above measurements are shown in Table 4. TABLE 4 Colorant (Dye No.)Hue Lightfastness Transparency This  9 ◯ ◯ ◯ invention This 10 ◯ ◯ ◯invention This  3B ◯ ◯ ◯ invention This  4B ◯ ◯ ◯ invention ComparativeC. I. Δ Δ Δ example Solvent. Yellow 162

[0218] As is apparent from the results in Table 4, since accurate colorreproduction and high OHP quality were obtained by using the color tonerof the present invention, the color toner of the present invention issuitable for use as a full-color toner. As the color toner of thepresent invention was excellent in light resistance, the color toner ofthe present invention can provide an image which can be preserved for along period of time.

Example 8

[0219] <Preparation of a Thermal Transfer Dye-Providing Material>

[0220] A coating composition for a thermal transfer dye-providing layerhaving the following composition was applied onto a surface of a 6μm-thick polyethylene terephthalate film (manufactured by Teijin Ltd.)whose back surface had been subjected to heat-resistant lubricatingtreatment, as a base, by wire-bar coating, to have a dry thickness of1.5 μm, thereby preparing a thermal transfer dye-providing material(5-1A) as an ink sheet.

[0221] Coating Composition for Thermal Transfer Dye-Donating Layer: Dye21 10 mmol Polyvinyl butyral resin 3 g (Denka Butyral 5000-A, tradename,manufactured by Denki Kagaku Kogyo K.K) Toluene 40 ml Methyl ethylketone 40 ml Polyisocyanate 0.2 ml (TAKENATE D110N, trade name,manufactured by Takeda Chemical Industries, Ltd.)

[0222] Other thermal transfer dye-providing materials (5-2A), (5-1B) and(5-2B) according to the present invention, and a thermal transferdye-providing material (5-3) for comparison were prepared in the samemanner as described above, except that the above Dye 21 was changed toanother dye, as shown in Table 5, respectively. (Preparation of athermal transfer image-receiving material)

[0223] The following composition was applied to a surface of a 150μm-thick synthetic paper (YUPO-FPG-150 (trade name) manufactured by OjiYuka Synthetic Paper Co., Ltd.) as a base, by wire-bar coating, to havea dry thickness of 8 μm, thereby preparing a thermal transferimage-receiving material. The thus-obtained coated film was pre-driedwith a drier, and then dried in an oven heated at 100° C. for 30minutes. Coating composition for an image-receiving layer: Polyesterresin (Vilon-280, trade name, 22 g manufactured by Toyobo Co., Ltd.)Polyisocyanate (KP-90, trade name, 4 g manufactured by Dainippon Ink andChemicals, Inc.) Amino-modified silicone oil (KF-857, trade 0.5 g name,manufactured by Shin-Etsu Silicones Co., Ltd.) Methyl ethyl ketone 85 mlToluene 85 ml Cyclohexanone 15 ml

[0224] Any of the thus-obtained thermal transfer dye-providing materials(5-1A), (5-2A), (5-1B), (5-2B) and (5-3) and the thermal transferimage-receiving material were placed one upon the other such that thethermal transfer dye-donating layer and the image-receiving layer werebrought into contact each other. Then, printing was performed from thesupport side of the thermal transfer dye-providing material, by using athermal head, under the conditions of a thermal head output of 0.25W/dot, a pulse width of 0.15 to 15 msec, and a dot density of 6 dots/mm,to fix, imagewise, a yellow dye on the image-receiving layer of theimage-receiving material. The maximum color density of the obtainedimage is shown in Table 5. A clear image without transfer unevennesscould be recorded with the thermal transfer dye-providing materials(5-1A), (5-2A), (5-1B) and (5-2B) according to the present invention.Then, the recorded thermal transfer image-receiving materials thusobtained were irradiated with Xe light (17,000 lx) for 5 days, toinvestigate the optical stability of a color image. The status Areflection density of a portion which showed a status A reflectiondensity of 1.0 after irradiation was measured, and the stability of theportion was evaluated in a retention rate (percentage) for a reflectiondensity of 1.0 before irradiation. The results are shown in Table 5.TABLE 5 Thermal transfer dye- Maximum providing color Fastness materialDye density to light Remarks 5-1A 21 1.8 91 This invention 5-2A 22 1.789 This invention 5-1B 38 2.2 100 This invention 5-2B 4B 2.4 99 Thisinvention 5-3 Dyed d for 1.8 52 Comparative comparison example Dye forcomparison d

[0225] As described above, the dyes of the present invention exhibitedsuperior fastness to light to the dye for comparison. Also, the dyes ofthe present invention had a bright hue.

Example 9

[0226] To prepare a color filter, a positive-type resist compositioncontaining a thermosetting resin, a quinonediazido compound, acrosslinking agent, a dye and a solvent was applied to a silicon waferby spin coating, and the resultant wafer was heated to evaporate thesolvent and then exposed to light through a mask to decompose thequinone diazido compound. The coated wafer was heated if necessary, andsubjected to development, to obtain a mosaic pattern. The exposure wascarried out using HITACHI LD-5010-i (NA=0.40) (trade name) i-rayexposure stepper manufactured by Hitachi, Ltd. SOPD or SOPD-B (eachtrade name) of Sumitomo Chemical Co., Ltd. was used as a developer.

[0227] <Preparation of Positive Resist Composition>

[0228] 3.4 parts by mass of a cresol novolak resin (mass averagemolecular weight of 4,300 in terms of polystyrene) obtained from amixture of: m-cresol/p-cresol/formaldehyde (reaction molarratio=5/5/7.5), 1.8 parts by mass of o-naphthoquinonediazido-5-sulfonicacid ester (two hydroxyl groups were esterified on average) preparedusing a phenol compound represented by the formula below, 0.8 parts bymass of hexamethoxymethylolmelamine, 20 parts by mass of ethyl lactate,and 1 part by mass of the dye of the present invention as shown in Table6 were mixed together, to obtain the positive resist composition.

[0229] <Preparation of a Color Filter>

[0230] After the thus-obtained positive resist composition was appliedto a silicon wafer by spin coating, the solvent was evaporated. Afterthe exposure, the silicon wafer was heated at 100° C., and the exposedportion was removed by alkali development, to obtain a positive coloredpattern having a resolution of 0.8 μm. The entire surface of thethus-obtained pattern was exposed to light, and then heated at 150° C.for 15 minutes, to obtain a yellow complementary color filter.

<Comparative Example>

[0231] A positive resist composition was obtained, by mixing 1 part bymass of Oleosol Yellow 2G (trade name) manufactured by Sumitomo ChemicalCo., Ltd., in place of the yellow dye of the present invention used inthe above Example. This positive resist composition was applied to asilicon wafer by spin coating, and then the solvent was evaporated.After exposure, the resulting silicon wafer was subjected to alkalidevelopment, to obtain a positive colored pattern having a resolution of1 μm. The entire surface of the thus-obtained pattern was exposed tolight, and then heated at 150° C. for 10 minutes, to obtain a yellowcolor filter.

[0232] <Evaluation>

[0233] The transmission spectrum of the thus-obtained yellow colorfilter was measured, to relatively evaluate the definitions (sharpness)on short-wavelength and long-wavelength sides of the spectrum, which areimportant for color reproduction. “◯” means an excellent level, “Δ”means a permissible level, and “X” means an impermissible level. As forlightfastness, the obtained image was irradiation with xenon light(85,000 lx) using a weather meter (Atras C. I65), for 7 days, to measurethe density of the image before and after irradiation with the xenonlight. Evaluation was carried out using the dye retention (remaining)rate [(density after irradiation/density before irradiation)×100%].TABLE 6 Absorption Light- Dye No. characteristics fastness This 21 ◯ 98%invention This 22 ◯ 96% invention This 3B ◯ 99% invention This 4B ◯ 99%invention Comparative Oleosol Δ 60% example Yellow 2G

[0234] It is understood that the dyes of the present invention wereexcellent in color reproduction, with sharp definitions on shortwavelength and long wavelength sides of the peak in interest of thespectrum, as compared with Comparative Example. It is also understoodthat the dyes of the present invention had excellent lightfastness, ascompared with the compound for comparison.

[0235] Having described our invention as related to the presentembodiments, it is our intention that the invention not be limited byany of the details of the description, unless otherwise specified, butrather be construed broadly within its spirit and scope as set out inthe accompanying claims.

What is claimed is:
 1. An ink, comprising at least one dye representedby formula (1):

wherein R¹, R² and R³ are each independently a hydrogen atom or amonovalent group; Z is a nitrogen atom, or a carbon atom to which ahydrogen atom or a monovalent group is bonded; and at least one of R¹,R², R³, and the monovalent group that Z has is a substituent having aheterocyclic group substituted with an azo group.
 2. The ink accordingto claim 1, wherein, in formula (1), one of R¹, R² and R³ represents asubstituent having a heterocyclic group substituted with an azo group.3. The ink according to claim 1, wherein, in formula (1), at least twoof R¹, R² and R³ each represent a substituent having a heterocyclicgroup substituted with an azo group.
 4. The ink according to claim 1,wherein the dye represented by formula (1) is a dye represented byformula (3):

wherein R¹⁰ is a hydrogen atom, an alkyl group, a cycloalkyl group, anaralkyl group, an alkoxy group or an aryl group; R¹¹ is a hydrogen atom,a halogen atom, a hydroxyl group, an alkoxy group, an amino group, asulfo group or a heterocyclic group; Het is an aromatic heterocyclicgroup; and R¹² is a hydrogen atom, a halogen atom, a hydroxyl group, analkoxy group, an amino group, a sulfo group, a heterocyclic group, or agroup represented by formula (3-1):

wherein, in formula (3-1), R^(10a) is a hydrogen atom, an alkyl group, acycloalkyl group, an aralkyl group, an alkoxy group or an aryl group;and Het is an aromatic heterocyclic group; in the formula (3), eachgroup on the dye may have a substituent.
 5. The ink according to claim4, wherein, in formula (3), R¹² is a hydrogen atom, a halogen atom, ahydroxyl group, an alkoxy group, an amino group, a sulfo group or aheterocyclic group.
 6. The ink according to claim 4, wherein, in formula(3), R¹² is a group represented by the formula (3-1).
 7. Anink-jet-recording method, comprising the step of: forming an image withan ink on an image-receiving material having an ink-receiving layercontaining white inorganic pigment particles on a support, wherein theink comprises at least one dye represented by formula (1):

wherein, in formula (1), R¹, R² and R³ are each independently a hydrogenatom or a monovalent group; Z is a nitrogen atom, or a carbon atom towhich a hydrogen atom or a monovalent group is bonded; and at least oneof R¹, R², R³, and the monovalent group that Z has is a substituenthaving a heterocyclic group substituted with an azo group.
 8. Theink-jet-recording method according to claim 7, wherein, in formula (1),one of R¹, R² and R³ represents a substituent having a heterocyclicgroup substituted with an azo group.
 9. The ink-jet-recording methodaccording to claim 7, wherein, in formula (1), at least two of R¹, R²and R³ each represent a substituent having a heterocyclic groupsubstituted with an azo group.
 10. The ink-jet-recording methodaccording to claim 7, wherein the dye represented by formula (1) is adye represented by formula (3):

wherein R¹⁰ is a hydrogen atom, an alkyl group, a cycloalkyl group, anaralkyl group, an alkoxy group or an aryl group; R¹¹ is a hydrogen atom,a halogen atom, a hydroxyl group, an alkoxy group, an amino group, asulfo group or a heterocyclic group; Het is an aromatic heterocyclicgroup; and R¹² is a hydrogen atom, a halogen atom, a hydroxyl group, analkoxy group, an amino group, a sulfo group, a heterocyclic group, or agroup represented by formula (3-1):

wherein, in formula (3-1), R^(10a) is a hydrogen atom, an alkyl group, acycloalkyl group, an aralkyl group, an alkoxy group or an aryl group;and Het is an aromatic heterocyclic group; in the formula (3), eachgroup on the dye may have a substituent.
 11. The ink-jet-recordingmethod according to claim 10, wherein, in formula (3), R¹² is a hydrogenatom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group,a sulfo group or a heterocyclic group.
 12. The ink-jet-recording methodaccording to claim 10, wherein, in formula (3), R¹² is a grouprepresented by the formula (3-1).
 13. A compound represented by formula(3):

wherein R¹⁰ is a hydrogen atom, an alkyl group, a cycloalkyl group, anaralkyl group, an alkoxy group or an aryl group; R¹¹ is a hydrogen atom,a halogen atom, a hydroxyl group, an alkoxy group, an amino group, asulfo group or a heterocyclic group; Het is an aromatic heterocyclicgroup; and R¹² is a hydrogen atom, a halogen atom, a hydroxyl group, analkoxy group, an amino group, a sulfo group, a heterocyclic group, or agroup represented by formula (3-1):

wherein, in formula (3-1), R^(10a) is a hydrogen atom, an alkyl group, acycloalkyl group, an aralkyl group, an alkoxy group or an aryl group;and Het is an aromatic heterocyclic group; in the formula (3), eachgroup on the compound may have a substituent.
 14. The compound accordingto claim 13, wherein, in formula (3), R¹² is a hydrogen atom, a halogenatom, a hydroxyl group, an alkoxy group, an amino group, a sulfo groupor a heterocyclic group.
 15. The compound according to claim 13,wherein, in formula (3), R¹² is a group represented by the formula(3-1).
 16. The compound according to claim 13, which is represented byformula (4):

wherein R¹⁰ is a hydrogen atom, an alkyl group, a cycloalkyl group, anaralkyl group, an alkoxy group or an aryl group; R¹¹ is a hydrogen atom,a halogen atom, a hydroxyl group, an alkoxy group, an amino group, asulfo group or a heterocyclic group; one of X and Y is a nitrogen atomand the other is a —C(—R¹³)═ group; R¹³ is a hydrogen atom, a halogenatom, a cyano group, an alkyl group, an alkylthio group, analkylsulfonyl group, an alkylsulfinyl group, an alkyloxycarbonyl group,a carbamoyl group, an alkoxy group, an aryl group, an arylthio group, anarylsulfonyl group, an arylsulfinyl group, an aryloxy group or anacylamino group; and R¹² is a hydrogen atom, a halogen atom, a hydroxylgroup, an alkoxy group, an amino group, a sulfo group, a heterocyclicgroup, or a group represented by formula (4-1):

wherein, in formula (4-1), R^(10a) is a hydrogen atom, an alkyl group, acycloalkyl group, an aralkyl group, an alkoxy group or an aryl group;and X and Y have the same meanings as those in formula (4); and in theformula (4), each group on the compound may have a substituent.
 17. Thecompound according to claim 16, wherein, in formula (4), R¹² is ahydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, anamino group, a sulfo group or a heterocyclic group.
 18. The compoundaccording to claim 16, wherein, in formula (4), R¹² is a grouprepresented by the formula (4-1).